TWI713574B - Materials for electronic devices - Google Patents

Abstract

The present application relates to a compound of a formula (I) or formula (II) which is suitable for use as functional material in an electronic device, especially as emitter material in an organic electroluminescent device.

Description

Materials for electronic devices

The present invention relates to compounds of formula (I) or (II), and to their use in electronic devices, especially organic electronic devices (OLED). The present invention further relates to specific embodiments of electronic devices including compounds of formula (I) or formula (II), and to methods for preparing compounds of formula (I) or formula (II).

The term "electronic device" according to the present invention is generally understood to refer to electronic devices containing organic materials. Preferably, it is understood to refer to OLED.

The general structure of OLED and its operation mode are known to those with ordinary knowledge in the technical field to which the invention belongs, and are described in particular in US 4539507, US 5151629, EP 0676461 and WO 1998/27136.

Regarding the performance data of electronic devices, further improvements are needed, especially for the wide range of commercial applications of electronic devices, such as displays or as light sources. In this respect, lifetime, efficiency, and operating voltage of the electronic device and the achieved color value are particularly important.

In the use of conventional white light sources and monitors, the total service life of the blue light-emitting components is the current limiting factor. Therefore, in the case of blue light-emitting OLEDs, there is potential to improve the life span of electronic devices and the color values achieved in the emitted light.

An important starting point for achieving the improvement is the selection of emitter compounds for electronic devices.

The prior art describes a variety of compounds as blue fluorescent emitter compounds, especially arylamines with a basic skeleton of indenopyridine. Examples of these are benzindenosylamines, for example according to WO 2008/006449 and WO 2007/140847.

In addition, WO 2007/018007 describes the use of nitrogen-containing heterocyclic derivatives. The compound is used as an emitter in an OLED with blue emission. However, in order to produce blue emission, the electronic device specified in WO 2007/018007 requires a high operating voltage of 6.0V.

Furthermore, EP 1860097 describes a variety of aromatic amine derivatives, and more specifically, includes compounds having a basic skeleton of indenofluoride. Indenochloride compounds are used in the hole transport layer in OLEDs with blue emission. However, in order to produce blue emission, the electronic device device specified in EP 1860097 requires a high operating voltage of 6.5V.

WO 2014/111269 describes a compound having a basic skeleton of benzindenopyridine. The compound is used as an emitter in the light-emitting layer of an electronic device (for example, an OLED with blue emission). In order to ensure that the electronic device is used for a display or a light source, it is advantageous to increase the efficiency of the electronic device.

In summary, the technical problem solved is therefore to provide a blue fluorescent emitter. More specifically, there is a need for compounds that can achieve favorable performance data for electronic devices. Preferably, the problem to be solved is to provide a compound that can achieve low operating voltage, high power efficiency, long life and/or blue emission in an electronic device into which the compound is introduced.

In the research of novel compounds for electronic devices, it has been unexpectedly found that the compounds of formula (I) or formula (II) with extended bis-indenopyridine basic skeleton are outstandingly suitable for use in electronic devices and particularly have blue Color coordinates, thus solving the technical problems presented above. The blue coordinate in the emitter compound is the height required for display and lighting applications, and it is also the height required for adjusting the color impression of various colors in displays or lighting applications.

The present invention thus provides compounds of formula (I) or formula (II)

Wherein: Ar ¹ is the same or different in each case and is an aryl or heteroaryl group, which has 6 to 18 aromatic ring atoms and may be substituted by one or more R ¹ groups; Ar ² in each case The following are the same or different and are aryl or heteroaryl groups, which have 6 aromatic ring atoms and may be substituted by one or more R ² groups; X ¹ is the same or different in each case and is BR ³ , C(R ³ ) ₂ , C(R ³ ) ₂ -C(R ³ ) ₂ -, C(R ³ ) ₂ -O-, C(R ³ ) ₂ -S-, -R ³ C=CR ^3- , R ³ C=N-, Si(R ³ ) ₂ , Ge(R ³ ) ₂ , -Si(R ³ ) ₂ -Si(R ³ ) ₂ -, C=O, O, S, Se, S= O, SO ₂ , NR ³ , PR ³ or P(=O)R ³ , wherein two or more R ³ groups can be combined with each other and can form a ring; R ¹ , R ² , R ^{3 are} in each case Same or different and are H, D, F, Cl, Br, I, C(=O)R ⁴ , CN, Si(R ⁴ ) ₃ , N(R ⁴ ) ₂ , P(=O)(R ⁴ ) ₂ , OR ⁴ , S(=O)R ⁴ , S(=O) ₂ R ⁴ , straight chain alkyl or alkoxy with 1 to 20 carbon atoms, branched chain with 3 to 20 carbon atoms or Cyclic alkyl or alkoxy groups, alkenyl or alkynyl groups having 2 to 20 carbon atoms, aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, or 5 to 30 aromatic rings atoms aryloxy or heteroaryl group, wherein each of the above groups may be substituted with one or more R ⁴ substituents, wherein the groups one or more CH ₂ groups may be -R ⁴ C =CR ⁴ -, C≡C, Si(R ⁴ ) ₂ , C=O, C=NR ⁴ , -C(=O)O-, -C(=O)NR ⁴ -, NR ⁴ , P(= O) (R ⁴ ), O, S, SO or SO ₂ replacement, wherein one or more of the hydrogen atoms in the above groups can be replaced by D, F, Cl, Br, I or CN, and wherein, two or More R ¹ , R ² , R ³ groups can be combined with each other and can form a ring; R ⁴ is the same or different in each case and is H, D, F, Cl, Br, I, C(=O)R ⁵ , CN, Si(R ⁵ ) ₃ , N(R ⁵ ) ₂ , P(=O)(R ⁵ ) ₂ , OR ⁵ , S(=O)R ⁵ , S(=O) ₂ R ⁵ , with A straight chain alkyl or alkoxy group with 1 to 20 carbon atoms, a branched or cyclic alkyl group or alkoxy group with 3 to 20 carbon atoms, an alkenyl or alkynyl group with 2 to 20 carbon atoms, An aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms or an aryloxy or heteroaryloxy group having 5 to 30 aromatic ring atoms, wherein each of the above groups may be connected to one or Multiple R ⁵ groups are substituted, Wherein, one or more CH ₂ groups in the above-mentioned groups can be controlled by -R ⁵ C=CR ⁵ -, -C≡C-, Si(R ⁵ ) ₂ , C=O, C=NR ⁵ , -C( =O)O-, C(=O)NR ⁵ , NR ⁵ , P(=O)(R ⁵ ), O, S, SO or SO ₂ replacement, wherein one or more hydrogen atoms in the above groups It can be replaced by D, F, Cl, Br, I or CN, and among them, two or more R ⁴ groups can be combined with each other and can form a ring; R ⁵ is the same or different in each case and is H, D, F, Cl, Br, I, CN, linear alkyl or alkoxy having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy having 3 to 20 carbon atoms, having 2 to Alkenyl or alkynyl with 20 carbon atoms, aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, or aryloxy or heteroaryloxy with 5 to 30 aromatic ring atoms , Wherein two or more R ⁵ groups can be bonded to each other and can form a ring; wherein, at least one of the two Ar ¹ groups must have 10 or more aromatic ring atoms.

For formula (I) or formula (II), the bond to the adjacent Ar ¹ or Ar ² group and to the X ¹ group may each exist in any position in the Ar ¹ or Ar ² group. More specifically, the expression method of formula (I) or formula (II) does not imply that the X ¹ groups must be in order to each other. The X ¹ groups can be in the cis position or the anti position to each other.

The following is a general definition of chemical groups in the text of this application: The aryl group in the text of the present invention contains 6 to 60 aromatic ring atoms. In the context of the present invention, the heteroaryl group contains 5 to 60 aromatic ring atoms, at least one of which is a heteroatom. The heteroatom is preferably selected from nitrogen (N), oxygen (O), sulfur (S), silicon (Si) and/or phosphorus (P), and more preferably selected from nitrogen (N), oxygen (O) ) And/or sulfur (S). These are basic definitions. If other priority considerations are listed in the description of the present invention, for example, regarding the number of aromatic ring atoms or the types of heteroatoms present, the same applies.

Aryl or heteroaryl here can be understood to mean a simple aromatic ring, namely benzene, or a simple heteroaromatic ring, for example, pyridine, pyrimidine or thiophene, or fused (annelated) aromatic or Heteroaromatic polycyclic ring, for example, naphthalene, phenanthrene, quinoline or carbazole. A fused (annelated) aromatic or heteroaromatic polycyclic ring is composed of two or more simple aromatic or heteroaromatic rings fused to each other in the context of this application.

、苝、丙二烯合茀、苯并蒽、苯并菲、稠四苯、稠五苯、苯并芘、呋喃、苯并呋喃、異苯并呋喃、二苯并呋 喃、噻吩、苯并噻吩、異苯并噻吩、二苯并噻吩、吡咯、吲哚、異吲哚、咔唑、吡啶、喹啉、異喹啉、吖啶、啡啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、啡噻

、啡

、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑(naphthimidazole)、菲并咪唑(phenanthrimidazole)、吡啶并咪唑(pyridimidazole)、吡

并咪唑(pyrazinimidazole)、喹喏啉并咪唑(quinoxalinimidazole)、

唑、苯并

唑、萘并

唑、蒽并

唑、菲并

唑、異

唑、1,2-噻唑、1,3-噻唑、苯并噻唑、嗒

、苯并嗒

、嘧啶、苯并嘧啶、喹喏啉、吡

、啡

、

啶、氮雜咔唑(azacarbazole)、苯并咔啉、啡啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-

二唑、1,2,4-

二唑、1,2,5-

二唑、1,3,4-

二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三

、1,2,4-三

、1,2,3-三

、四唑、1,2,4,5-四

、1,2,3,4-四

、1,2,3,5-四

、嘌呤、喋啶、吲

及苯并噻二唑，或這些基團的組合。 Aryl or heteroaryl (each of which can be substituted by the above-mentioned groups and can be bound to an aromatic or heteroaromatic system via any desired position) is particularly understood to mean groups derived from the following: benzene, naphthalene, Onion, phenanthrene, pyrene, dihydropyrene,

, Perylene, allene pyrene, benzanthracene, triphenylene, thick tetrabenzene, thick pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene , Isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo -6,7-quinoline, benzo-7,8-quinoline, phenanthrene

,coffee

, Pyrazole, indazole, imidazole, benzimidazole, naphthimidazole (naphthimidazole), phenanthrimidazole (phenanthrimidazole), pyridimidazole (pyridimidazole), pyridine

Pyrazinimidazole, quinoxalinimidazole,

Azole, benzo

Azole, naphtho

Azole, anthracene

Azole, phenanthrene

Azole, iso

Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole,

Benzota

, Pyrimidine, benzopyrimidine, quinoline, pyridine

,coffee

,

Pyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-

Diazole, 1,2,4-

Diazole, 1,2,5-

Diazole, 1,3,4-

Diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazole

, 1,2,4-three

, 1,2,3-three

, Tetrazole, 1,2,4,5-tetra

, 1,2,3,4-four

,1,2,3,5-four

, Purine, pteridine, indino

And benzothiadiazole, or a combination of these groups.

The aryloxy group defined in the present invention is understood to mean the above-defined aryl group bonded via an oxygen atom. A similar definition applies to heteroaryloxy.

。 The aromatic ring system in the context of the present invention contains 5 to 60 aromatic carbon atoms in the ring system. The heteroaromatic ring system in the context of the present invention contains 5 to 60 aromatic ring atoms, of which at least one ring atom is a heteroatom. The heteroatom is preferably selected from nitrogen (N), oxygen (O), sulfur (S), silicon (Si) and/or phosphorus (P), and more preferably selected from nitrogen (N), oxygen (O) ) And/or sulfur (S). This is the basic definition. If other priority considerations are listed in the description of the present invention, for example, regarding the number of aromatic ring atoms or the number or types of heteroatoms present, these may apply. The aromatic or heteroaromatic ring system in the context of the present invention is understood to mean a system that does not necessarily contain only aryl or heteroaryl, but it may also consist of non-aromatic units (preferably less than 10% of non-H Atom) bonds two or more aryl or heteroaryl groups, for example, sp ³ -mixed carbon, silicon, nitrogen or oxygen atom, sp ² -mixed carbon or nitrogen atom or sp- mixed carbon atom. For example, systems such as 9,9'-spirobifluorene, 9,9'-diaryl stilbene, triarylamine, diaryl ether, stilbene, etc. are also considered to be aromatic rings in the context of the present invention Systems, and similar systems, in which two or more aryl groups are bonded by linear or cyclic alkyl, alkenyl or alkynyl groups, or by silyl groups, for example. In addition, a system in which two or more aryl or heteroaryl groups are bonded to each other via a single bond is also regarded as an aromatic or heteroaromatic ring system in the context of the present invention, for example, biphenyl, terphenyl or diphenyl Phenyl Tri

.

、苝、丙二烯合茀、稠四苯、稠五苯、苯并芘、聯苯、伸聯苯、聯三苯、伸聯三苯、聯四苯、茀、螺二茀(spirobifluorene)、二氫菲、二氫芘、四氫芘、順-或反-茚并茀、參茚并苯(truxene)、異參茚并苯(isotruxene)、螺參茚并苯(spirotruxene)、螺異參茚并苯(spiroisotruxene)、呋喃、苯并呋喃、異苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、異苯并噻吩、二苯并噻吩、吡咯、吲哚、異吲哚、咔 唑、吲哚并咔唑、茚并咔唑、吡啶、喹啉、異喹啉、吖啶、啡啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、啡噻

、啡

、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑(naphthimidazole)、菲并咪唑(phenanthrimidazole)、吡啶并咪唑(pyridimidazole)、吡

并咪唑(pyrazinimidazole)、喹喏啉并咪唑(quinoxalinimidazole)、

唑、苯并

唑、萘并

唑、蒽并

唑、菲并

唑、異

唑、1,2-噻唑、1,3-噻唑、苯并噻唑、嗒

、苯并嗒

、嘧啶、苯并嘧啶、喹喏啉、1,5-二吖蒽、2,7-二氮雜芘(diazapyrene)、2,3-二氮雜芘、1,6-二氮雜芘、1,8-二氮雜芘、4,5-二氮雜芘、4,5,9,10-四氮雜苝、吡

、啡

、啡

、啡噻

、茀魯並(fluorubine)、

啶、氮雜咔唑(azacarbazole)、苯并咔啉、啡啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-

二唑、1,2,4-

二唑、1,2,5-

二唑、1,3,4-

二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三

、1,2,4-三

、1,2,3-三

、四唑、1,2,4,5-四

、1,2,3,4-四

、1,2,3,5-四

、嘌呤、喋啶、吲

及苯并噻二唑、或這些基團的組合。 The aromatic or heteroaromatic ring system having 5 to 60 aromatic ring atoms and in each case can be substituted by the above-defined group and can be bonded to the aromatic or heteroaromatic system via any desired position is particularly It is understood to refer to groups derived from the following: benzene, naphthalene, onion, benzanthracene, phenanthrene, triphenylene, pyrene,

, Perylene, allene pyrene, thick tetrabenzene, thick pentacene, benzopyrene, biphenyl, biphenyl, terphenyl, terphenyl, bitetraphenyl, fen, spirobifluorene, Dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenopyrene, truxene, isotruxene, spirotruxene, spirotruxene Indenobenzene (spiroisotruxene), furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole , Indolocarbazole, indenocarbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo- 7,8-quinoline, phenothi

,coffee

, Pyrazole, indazole, imidazole, benzimidazole, naphthimidazole (naphthimidazole), phenanthrimidazole (phenanthrimidazole), pyridimidazole (pyridimidazole), pyridine

Pyrazinimidazole, quinoxalinimidazole,

Azole, benzo

Azole, naphtho

Azole, anthracene

Azole, phenanthrene

Azole, iso

Azole, 1,2-thiazole, 1,3-thiazole, benzothiazole,

Benzota

, Pyrimidine, benzopyrimidine, quinoline, 1,5-diazanthene, 2,7-diazapyrene (diazapyrene), 2,3-diazapyrene, 1,6-diazapyrene, 1 ,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperylene, pyrene

,coffee

,coffee

Phenothi

, Fluorubine,

Pyridine, azacarbazole, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-

Diazole, 1,2,4-

Diazole, 1,2,5-

Diazole, 1,3,4-

Diazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 1,3,5-triazole

, 1,2,4-three

, 1,2,3-three

, Tetrazole, 1,2,4,5-tetra

, 1,2,3,4-four

,1,2,3,5-four

, Purine, pteridine, indino

And benzothiadiazole, or a combination of these groups.

In the context of the present invention, a linear alkyl group having 1 to 20 carbon atoms, or a branched or cyclic alkyl group having 3 to 20 carbon atoms, or an alkenyl or alkynyl group having 2 to 20 carbon atoms means Among them, individual hydrogen atoms or CH ₂ groups may also be substituted by the above-mentioned groups in the group definition. This is the basic definition. If other priority considerations are listed in the description of the invention, for example, with regard to the number of carbon atoms, the same applies. Preferably, straight-chain alkyl groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, and alkenyl or alkynyl groups having 2 to 20 carbon atoms are understood to be Refers to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, 2-methylbutyl, n-pentyl, second pentyl, ring Pentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2, 2,2-Trifluoroethyl, vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, Cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, or octynyl. Alkoxy or thioalkyl groups having 1 to 20 carbon atoms are preferably understood to be methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy Group, isobutoxy, second butoxy, second butoxy, n-pentoxy, second pentoxy, 2-methylbutoxy, n-hexyloxy, cyclohexyloxy, n-heptoxy Group, cycloheptyloxy, n-octyloxy, cyclooctyloxy, 2-ethylhexyloxy, pentafluoroethoxy, 2,2,2-trifluoroethoxy, methylthio , Ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, second butylthio, second butylthio, n-pentylthio, The second pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, three Fluoromethylthio, pentafluoroethylthio, 2,2,2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentan Alkenylsulfanyl, hexenylsulfanyl, cyclohexenylsulfanyl, heptenylsulfanyl, cycloheptenylsulfanyl, octenylsulfanyl, cyclooctenylsulfanyl, ethynylsulfanyl, propyl Alkynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio, or octynylthio.

In the text of this application, the term that two or more groups can form a ring together should be understood as referring to two groups that are bonded to each other particularly by a chemical bond. This is illustrated by the following reaction diagram:

However, in addition, the above terms should also be understood to mean that if one of the two groups is hydrogen, the second group is bonded to the position where the hydrogen atom is bonded to form a ring. This is illustrated by the following reaction diagram:

The terms that two or more groups can form a ring together shall be understood in the text of this application to mean that, especially in the sense of the present invention, two groups can form an aryl group, a heteroaryl group, an aryloxy group, a heteroaryl group. Alkyloxy, aromatic or heteroaromatic ring system, or cyclic alkyl, alkenyl or alkynyl.

Preferably the compound corresponds to formula II:

The groups occurring therein are as defined above.

Preferably, the bonding in the Ar ² group to the adjacent Ar ¹ or Ar ² group is each in a para position to each other.

Preferably the Ar ¹ group is the same or different in each case and is selected from: aryl or heteroaryl having 6 to 14 aromatic ring atoms, more preferably 6 to 10 aromatic ring atoms , Wherein each of the Ar ¹ groups may be substituted by one or more R ¹ groups.

Preferably the Ar ² group is phenyl, which may be substituted with one or more R ² groups.

In a particularly preferred embodiment, the Ar ¹ group is naphthyl, which may be substituted by one or more R ¹ groups, and the Ar ² group is phenyl, which may be substituted by one or more R ² groups.

In a particularly preferred embodiment, one of the two Ar ¹ groups is phenyl, which may be substituted with one or more R ¹ groups, and the other of the two Ar ¹ groups is naphthalene Group, which may be substituted with one or more R ¹ groups, and the Ar ² group is phenyl, which may be substituted with one or more R ² groups.

Preferably X ¹ is the same or different in each case and is selected from C(R ³ ) ₂ , -C(R ³ ) ₂ -C(R ³ ) ₂ -, -C(R ³ ) ₂ -O -, -R ³ C=CR ³ -, Si(R ³ ) ₂ , C=O, O, S, S=O, SO ₂ , and NR ³ , wherein two or more R ³ groups can be combined with each other Can form a ring. More preferably, X ¹ is selected from C(R ³ ) ₂ , -C(R ³ ) ₂ -C(R ³ ) ₂ -, -C(R ³ ) ₂ -O-, Si(R ³ ) ₂ , O, S, and NR ³ , wherein two or more R ³ groups can be combined with each other and can form a ring. Most preferably, X ¹ is C(R ³ ) ₂ .

Preferably, R ¹ and R ² are the same or different in each case and are H, D, F, CN, Si(R ⁴ ) ₃ , a linear alkyl group having 1 to 20 carbon atoms or an alkoxy group Groups, branched or cyclic alkyl or alkoxy groups with 3 to 20 carbon atoms, or aromatic or heteroaromatic ring systems with 5 to 20 aromatic ring atoms, wherein each of the above groups can be Or more R ⁴ groups, and wherein one or more CH ₂ groups in the above groups can be through -C≡C-, -R ⁴ C=CR ⁴ , Si(R ⁴ ) ₂ , C=O, NR ⁴ , O or S replacement.

More preferably, R ¹ is the same or different in each case and is selected from H, CN, N(R ⁴ ) ₂ and aromatic or heteroaromatic ring systems having 5 to 30 aromatic ring atoms, wherein , The above groups may each be substituted with one or more R ⁴ groups.

More preferably, R ² is H or D, more preferably H.

Preferably, R ³ is the same or different in each case and is F, CN, Si(R ⁴ ) ₃ , a linear alkyl group or alkoxy group having 1 to 20 carbon atoms, having 3 to 20 carbon atoms A branched or cyclic alkyl or alkoxy group of carbon atoms, or an aromatic or heteroaromatic ring system having 5 to 20 aromatic ring atoms, wherein the above-mentioned groups may each be through one or more R ⁴ groups And wherein, one or more CH ₂ groups in the above groups can be controlled by -C≡C-, -R ⁴ C=CR ⁴ -, Si(R ⁴ ) ₂ , C=O, NR ⁴ , O or S Alternatively, or wherein, two or more R ³ groups may be bonded to each other and may form a ring.

In preferred embodiments, R ³ is the same or different in each case and is a straight chain alkyl group having 1 to 20 carbon atoms or a branched chain alkyl group having 3 to 20 carbon atoms. More preferably, R ³ is a straight-chain alkyl group having 5 to 12 carbon atoms.

In a preferred embodiment, the two R ³ groups that are part of the X ¹ group (which is C(R ³ ) ₂ or Si(R ³ ) ₂ ) form a ring with each other, resulting in a spiro compound. This preferably forms a five- or six-membered ring. In addition, preferably in this case, the R ³ group is an alkyl group, thus forming a spirocyclic alkyl ring, more preferably a spirocyclohexane ring or a spirocyclopentane ring.

Preferably, R ⁴ is the same or different in each case and is F, CN, Si(R ⁵ ) ₃ , linear alkyl or alkoxy having 1 to 20 carbon atoms, having 3 to 20 A branched or cyclic alkyl or alkoxy group with carbon atoms, or an aromatic or heteroaromatic ring system with 5 to 20 aromatic ring atoms, wherein the above-mentioned groups can each be connected to one or more R ⁵ groups And wherein, one or more CH ₂ groups in the above groups can be replaced by -C≡C-, -R ⁵ C=CR ⁵ -, Si(R ⁵ ) ₂ , C=O, NR ⁵ , O and S is substituted, or two or more R ⁴ groups can be combined with each other and can form a ring.

In a preferred embodiment of the present invention, the R ¹ and R ² groups in formula (I) or formula (II) are H or D, more preferably H.

In another preferred embodiment of the present invention, one or more R ¹ groups are CN; more preferably, exactly two R ¹ groups are CN.

In another preferred embodiment of the present invention, one or more R ¹ groups are aromatic or heteroaromatic ring systems with 6 to 20 aromatic ring atoms and may be substituted by one or more R ⁴ groups; More preferably, exactly two R ¹ groups are aromatic or heteroaromatic ring systems having 6 to 20 aromatic ring atoms and may be substituted by one or more R ⁴ groups.

In a particularly preferred embodiment, R ¹ is phenyl, naphthyl, carbazole, benzocarbazole, dibenzofuran, benzofuran, fen or green onion, each of which may be substituted by R ⁴ group.

In another preferred embodiment of the present invention, none of the R ¹ and R ² groups is a group of formula N(R ⁴ ) ₂ . In this case, preferably, the X ¹ group is not NR ³ ; more preferably, the X ¹ group is C(R ³ ) ₂ in this case.

In another preferred embodiment of the present invention, one or more R ¹ groups are N(R ⁴ ) ₂ , and more preferably, exactly two R ¹ groups are N(R ⁴ ) ₂ .

The preferred embodiment of the compound corresponds to formula (II-1)

Wherein: Z ¹ is the same or different in each case and is CR ¹ or N, wherein when a group is attached, Z ¹ is C; Z ² is the same or different in each case and is CR ² or N, wherein when a group is attached, Z ² is C; and the X ¹ group is as defined above.

The preferred embodiment of compound substitution corresponds to formula (II-2)

Wherein: Z ¹ is the same or different in each case and is CR ¹ or N, wherein when a group is attached, Z ¹ is C; Z ² is the same or different in each case and is CR ² or N, wherein when a group is attached, Z ² is C; and the X ¹ group is as defined above.

For formulas (II-1) and (II-2), the bond to the X ¹ group and the bond between the aromatic rings can each exist at any position of the aromatic ring, as can be between individual aromatics The bond between the rings. More specifically, the expressions of formulas (II-1) and (II-2) do not imply that the X ¹ groups must be in order of each other. The X ¹ groups can be in the sequence or anti-position of each other.

Preferably, no more than two Z ¹ groups per aromatic ring are N, more preferably no more than one Z ¹ group per aromatic ring is N, and more preferably no Z ¹ groups in any aromatic ring are N.

Generally preferably Z ¹ is CR ¹ .

Preferably, no more than two Z ² groups per aromatic ring are N, more preferably no more than one Z ² group per aromatic ring is N, and more preferably no Z ² groups in any aromatic ring are N.

Generally preferably Z ² is CR ² .

Preferred embodiments of formula (II-1) or (II-2) correspond to the following formulas (II-1-1) to (II-1-20), or (II-2-1) to (II-2) -9)

Wherein: Z ¹ is the same or different in each case and is CR ¹ or N; Z ² is the same or different in each case and is CR ² or N; and the X ¹ group is as defined above.

More specifically, for the Z ¹ , Z ² and X ¹ groups, the above-specified preferred embodiments are also preferable for the above formula.

Again, particularly preferably, in formulas (II-1-1) to (II-1-20) and (II-2-1) to (II-2-9), Z ¹ is CR ¹ , Z ² is CR ² , and X ¹ is C(R ³ ) ₂ .

Among formulas (II-1-1) to (II-1-20) and (II-2-1) to (II-2-9), formula (II-1-4) is particularly preferred.

Preferably, the compound of formula (II) corresponds to formula (II-1-4-1)

Wherein, X ¹ and R ¹ are as defined above.

Preferably, X in formula (II-1-4-1) is the same or different in each case and is selected from C(R ³ ) ₂ , -C(R ³ ) ₂ -C(R ³ ) ₂ -, -C(R ³ ) ₂ -O-, -Si(R ³ ) ₂ , O, S, and NR ³ ; more preferably, X ¹ is C(R ³ ) ₂ .

Preferably, R ¹ in formula (II-1-4-1) is the same or different in each case and is H, D, F, CN, Si(R ⁴ ) ₂ , Si(R ⁴ ) ₃ , N(R ⁴ ) ₂ , or an aromatic or heteroaromatic ring system (which has 5 to 20 aromatic ring atoms and in each case may be substituted by one or more R ⁴ groups).

In a particularly preferred embodiment, R ¹ in formula (II-1-4-1) is phenyl, naphthyl, carbazole, benzocarbazole, dibenzofuran, benzofuran, fennel or green onion , Each of them may be substituted by R ⁴ groups.

Very particularly good specific examples of the compound of formula (II) correspond to the following formula, wherein, preferably: Z ¹ is CR ¹ and Z ² is CR ² :

Preference is given to administering the following compounds of formula (I) or formula (II):

The following compounds are examples of compounds of formula (I) or formula (II):

The compound of formula (I) or formula (II) can be prepared from methods or reaction steps known in organic chemistry.

The preferred method for preparing the compound of formula (I) or formula (II) is shown in the following (reaction diagram 1):

Ar: aromatic or heteroaromatic group

X: bridging group

X*: the precursor group of the bridging group

Y*: Reactive group, for example, Cl, Br, I

For this purpose, the introduction of reactive groups leads to compounds (formula 1), which in many cases are commercially available, for example, by bromination, or by bromination and subsequent boronization. Then, a double coupling reaction is carried out, for example, the Suzuki coupling reaction, in which two additional aromatic groups are introduced. These additional aromatic groups contain functional X* groups, which can achieve ring closure to form bridging X groups. After the ring-closing reaction, a compound of formula (I) or formula (II) (formula 4 in reaction diagram 1) is obtained, which may be further functionalized if necessary.

The details of the method described above in the form of reaction diagrams can also be found in the working examples.

Those with ordinary knowledge in the technical field to which the invention pertains can deviate from or modify the above-described methods described in the form of reaction diagrams to achieve the compounds of formula (I) or formula (II), if this is necessary. This is within the general ability of a person with general knowledge in the technical field to which the invention belongs.

This application therefore provides a method for preparing a compound of formula (I) or formula (II), which is characterized in that it includes at least one metal-catalyzed coupling reaction and at least one ring-closing reaction. The metal-catalyzed coupling reaction is preferably a transition metal-catalyzed coupling reaction, more preferably a Suzuki reaction.

Reaction Figure 2 shows a method for preparing a compound of formula (I) or formula (II).

Response Chart 2

The above-mentioned synthesis method according to Reaction Figure 2 can be followed by a further functionalization reaction, wherein the obtained compound of the present invention is further transformed.

The above-mentioned compounds of the present invention, especially compounds substituted with reactive leaving groups (such as bromine, iodine, chlorine, boric acid or boric acid esters) can find use as monomers for the production of corresponding oligomers, dendrimers or polymer. Suitable reactive leaving groups are, for example, sulfonate (for example, tosylate or triflate), bromine, iodine, chlorine, boric acid, boronic ester, amine, double Bond or CC triple bond alkenyl or alkynyl, Oxetane (oxirane), oxetane (oxetane), groups that enter the cycloaddition (for example, 1,3-dipolar cycloaddition), for example, dienes or azides Chemicals, carboxylic acid derivatives, alcohols and silanes.

The present invention preferably encompasses oligomers, polymers or dendrimers comprising one or more compounds of formula (I) or formula (II), wherein to the polymer, oligomer or dendrimer The bond can be located at any desired position, and it is substituted by R ¹ or R ² in formula (I) or formula (II).

According to the linkage of the compound of formula (I) or formula (II), the compound is part of the side chain of the oligomer or polymer or part of the main chain. In the context of the present invention, oligomer is understood to mean a compound formed from at least three monomer units. In the context of the present invention, a polymer is understood to mean a compound formed by at least ten monomer units. The polymer, oligomer or dendrimer of the present invention can be conjugated, partially conjugated or non-conjugated. The oligomer or polymer of the present invention can be linear, branched or dendritic. In the structure with linear linkage, the units of formula (I) or formula (II) can be directly bonded to each other, or they can be bonded to each other via a divalent group, for example, via a substituted or unsubstituted alkylene group Group, via a heteroatom or via a divalent aromatic or heteroaromatic group. In branched and dendritic structures, it is possible, for example, for three or more units of formula (I) or formula (II) to be combined via trivalent or higher valence groups, for example, via trivalent or higher High-valent aromatic or heteroaromatic groups to provide branched or dendritic oligomers or polymers.

For the repeating units of formula (I) or formula (II), in oligomers, dendrimers and polymers, the same priority considerations apply to compounds of formula (I) or formula (II) as described above.

For preparing oligomers or polymers, the monomers of the present invention are homopolymerized or copolymerized with other monomers. Appropriate and preferred co-monomer systems are selected from the group consisting of: 茀 (for example: EP 842208 or WO 2000/22026), spirobifluorene (for example: EP 707020, EP 894107 or WO 2006/ 061181), p-phenylene (for example: WO 1992/18552), carbazole (for example: WO 2004/070772 or WO 2004/113468), thiophene (for example: EP 1028136), dihydrophenanthrene (for example: WO 2005/014689 Or WO 2007/006383), cis-and trans-indenopyridine (for example: WO 2004/041901 or WO 2004/113412), ketone (for example: WO 2005/040302), phenanthrene (for example: WO 2005/104264 or WO 2007 /017066), or from multiple of these units. Polymers, oligomers and dendrimers typically contain further units, for example, emitting (fluorescent or phosphorescent) units, for example, vinyl triarylamine (e.g. WO 2007/068325) or phosphorescent metal Compounds (e.g. WO 2006/003000) and/or charge transport units, especially those based on triarylamine.

The polymers, oligomers, and dendrimers of the present invention are generally prepared by polymerizing one or more monomer classes, where at least one monomer results in a repeating unit of formula (I) or formula (II) in the polymer. Appropriate polymerization reactions are known to those with ordinary knowledge in the technical field to which the invention belongs and are described in the literature. A particularly suitable and preferred polymerization reaction leading to C-C and C-N bonding is as follows: (A) SUZUKI polymerization; (B) YAMAMOTO polymerization; (C) STILLE polymerization; (D) HARTWIG-BUCHWALD polymerization; (E) NEGISHI polymerization; and (F) HIYAMA polymerization.

How the polymerization can be carried out by these methods and how the polymer can then be separated and purified from the reaction medium is known to those with ordinary knowledge in the technical field to which the invention belongs and is described in detail in the literature, for example in WO 2003/048225, WO 2004/037887 and WO 2004/037887.

For processing the compound of the present invention from the liquid phase, for example, by spin coating or by printing, the compound of the present invention needs to be formulated. These formulations can be, for example, solutions, dispersions or emulsions. For this purpose, a mixture of two or more solvents can be preferably used. Suitable and preferred solvents are for example: toluene, anisole, ortho, meta or p-xylene, methyl benzoate, mesitylene, tetralin, veratrole , THF, methyl-THF, THP, chlorobenzene, dioxane (dioxane), phenoxytoluene (especially 3-phenoxytoluene), (-)-fenchone ((-)-fenchone ), 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2 -Pyrrolidone, 3-methylanisole, 4-methylanisole, 3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol , Benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indene, benzoic acid Methyl ester, NMP, p-cymene, ethyl phenyl ether (phenetole), 1,4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethyl Glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol diyl ether, tetraethylene glycol dimethyl ether, 2-iso Propylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane or mixtures of these solvents.

The present invention therefore further provides formulations, especially solutions, dispersions or emulsions, which comprise at least one compound of formula (I) or formula (II), or at least one polymer comprising at least one unit of formula (I) or formula (II) , Oligomer or dendrimer, and at least one solvent, preferably an organic solvent. The manner in which this type of solution can be prepared is known to those with ordinary knowledge in the technical field to which the invention belongs and is described, for example, in WO 2002/072714, WO 2003/019694 and the documents cited therein.

The compound of formula (I) or formula (II) is suitable for use in electronic devices, especially in organic electroluminescent devices (OLED). Depending on the substitution, the compound is used for different functions and layers.

The compound of formula (I) or formula (II) can be used for any function in an organic electroluminescence device, for example, as a hole transport material, as a host material, as a luminescent material, or as an electron transport material. Preferably, the compound of formula (I) or formula (II) can be used as a host material or as a luminescent material, more preferably as a luminescent material. The present invention therefore further provides the use of the compound of formula (I) or formula (II) in electronic devices. The electronic device is preferably selected from the group consisting of: organic integrated circuit (OIC), organic field effect transistor (OFET), organic thin film transistor (OTFT), organic light emitting transistor (OLET), organic solar Battery (OSC), organic optical detector, organic photoreceptor, organic field quenching device (OFQD), organic light emitting device Chemical components (OLEC), organic laser diodes (O-lasers) and more preferably selected from organic electroluminescent devices (OLEDs).

The present invention further provides an electronic device including at least one compound of formula (I) or formula (II). The electronic device is preferably selected from the devices specified above. Special priority considerations are given to organic electroluminescent devices including anode, cathode and at least one light-emitting layer, characterized in that at least one organic layer of the organic electroluminescent device includes at least one compound of formula (I) or formula (II), or at least one of the foregoing Oligomer, polymer or dendrimer.

In addition to the cathode, the anode, and the light-emitting layer, the organic electroluminescent device can also include more layers. These in each case are selected from, for example, one or more hole injection layer, hole transport layer, hole blocking layer, electron transport layer, electron injection layer, electron blocking layer, exciton blocking layer, intermediate layer , Charge generation layer (IDMC 2003, Taiwan; Session 21 OLED (5), T. Matsumoto, T. Nakada, J. Endo, K. Mori, N. Kawamura, A. Yokoi, J. Kido, Multiphoton Organic EL Device Having Charge Generation Layer ) and/or organic or inorganic p/n junction. At the same time, it is not necessary for each of these layers to exist, and the choice of the layer depends on the compound used and in particular also depends on whether the device is a fluorescent or phosphorescent electroluminescent device.

The order of the layers in the organic electroluminescence device is preferably as follows: anode-hole injection layer-hole transport layer-light emitting layer-electron transport layer-electron injection layer-cathode. Not all of these layers are necessarily present here, and in addition, there may be additional layers, for example, an electron blocking layer (a light-emitting layer adjacent to the anode side), or a hole blocking layer (a light-emitting layer adjacent to the cathode side) .

Preferably, the electronic device provided by the present invention includes an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode, wherein the compound of formula (I) or formula (II) is preferably Exist in the light-emitting layer.

The present invention preferably covers an electronic device, including an emission layer, the emission layer includes compound H1 or H2 and a compound of formula (I) or formula (II), preferably compound D1, D2, D3 or D4, and includes compound ETL The electron transport layer.

The organic electroluminescent device of the present invention preferably includes a light-emitting layer, which is in the blue region with a wavelength range between 420nm and 490nm Has the maximum emission.

The organic electroluminescent device of the present invention may include two or more light-emitting layers. More preferably, in this case, these emission layers generally have several emission maxima between 380nm and 750nm, so that the overall result is white emission; in other words, use fluorescent or phosphorescent and emit blue and green , Yellow, orange or red light-emitting compounds in the light-emitting layer. Particularly preferred is a three-layer system, that is, a system with three light-emitting layers, wherein preferably at least one of these layers includes at least one compound of formula (I) or formula (II), and wherein the three layers show blue , Green, yellow, orange or red emission (for basic structure, see for example WO 2005/011013). It should be noted that for the production of white light, instead of using a plurality of light-emitting emitter compounds, it may also be appropriate to individually use emitter compounds that emit in a wide wavelength range.

Alternatively and/or additionally, the compounds of the present invention may also exist in the hole transport layer or in another layer in these organic electroluminescent devices. The various light-emitting layers can be directly adjacent to each other, or they can be separated from each other by non-light-emitting layers. In the preferred embodiment of the present invention, the white light-emitting OLED is called tandem OLED, which means that two or more complete OLED layers are sequentially present in the OLED. The OLED layer sequence includes a hole transport layer, a light emitting layer, and an electron transport layer. Each of them is separated by the charge generation layer.

It is preferable to use the compound of formula (I) or formula (II) in the light-emitting layer. More specifically, the compound of formula (I) or formula (II) is suitable for use as a light-emitting compound or as a host material in a light-emitting layer.

The compounds of the present invention are particularly suitable for use as blue light-emitting emitter compounds or as host compounds for blue light-emitting emitter compounds. in In this case, the electronic device in question may include a single light-emitting layer (including the compound of the present invention), or two or more light-emitting layers. The additional light-emitting layer may include one or more compounds of the present invention or other compounds.

When the compound of the present invention is used as the host material in the OLED light-emitting layer, preferably none of the R ¹ , R ² and R ³ substituents are selected from those conjugated with the basic skeleton of formula (I) or formula (II) Groups, and more particularly, none of the R ¹ , R ² and R ³ substituents are selected from cyano, arylamino or aryl or heteroaryl. More preferably, in the case of using the compound of the present invention as the matrix material, R ¹ and R ² are selected from: H, D, F and an alkyl group having 1 to 10 carbon atoms, more preferably selected from H and D ; Best, R ¹ and R ² are H.

When the compound of the present invention is used as the emitter compound in the OLED light-emitting layer, preferably one or more R ¹ , R ² and R ³ substituents are selected from the basic skeleton of formula (I) or formula (II) Conjugated groups, for example, cyano, arylamino or aryl or heteroaryl.

When the compound of the present invention is used as the light-emitting compound in the light-emitting layer, it is preferably used in combination with one or more host materials. The host material here is understood to mean a material present in the light-emitting layer, preferably as a main component, and does not emit light during device operation.

The proportion of the luminescent compound in the luminescent layer mixture is between 0.1% and 50.0%, preferably between 0.5% and 20.0%, and more preferably between 1.0% and 10.0%. Correspondingly, the ratio of the matrix material is between 50.0% and 99.9%, preferably between 80.0% and 99.5%, and more preferably between 90.0% and 99.0%.

When applying the compound from the gas phase, use% as the ratio figure It is understood in the text of this application to mean% by volume, and when the compound is applied from a solution,% by weight is meant.

If the compound of the present invention is used as a host material, it can be used in combination with any known luminescent compound. Preferably, it is used in combination with the preferred luminescent compound specified below, especially, with the preferred fluorescent compound specified below.

If the compound of formula (I) or formula (II) is used as a host material in combination with a phosphorescent emitter in the light-emitting layer, the phosphorescent emitter is preferably selected from the phosphorescent emitter categories and specific examples listed below. Furthermore, in this case, preferably one or more additional host materials are present in the light-emitting layer.

This "mixed matrix system" preferably includes two or three different matrix materials, more preferably two different matrix materials. Preferably, in this case, one of the two materials is a material with hole transport properties and the other material is a material with electron transport properties. Preferably, the compound of formula (I) or formula (II) is a material with hole transport properties.

However, the desired electron transport and hole transport properties of the mixed matrix components can also be mainly or completely combined in a single mixed matrix component. In this case, the additional mixed matrix components fill other functions. The two different matrix materials can be present in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, more preferably 1:10 to 1:1, and most preferably 1:4 to 1:1. Priority consideration is given to the use of mixed matrix systems in phosphorescent organic electroluminescent devices. One source for more detailed information about mixed matrix systems is application WO 2010/108579.

Can be used in combination with the compound of the present invention as a mixed matrix system The particularly suitable matrix material for the matrix components of the system is selected from the following: the preferable matrix materials for phosphorescent luminescent compounds or the preferable matrix materials for fluorescent luminescent compounds, depending on what type of luminescent compound is used for the mixed matrix system.

The compound of the present invention can also be used in other layers, for example, as a hole transport material in a hole injection or hole transport layer or an electron blocking layer.

If the compound of formula (I) or formula (II) is used as the hole transport material, for example, in the hole transport layer, hole injection layer or electron blocking layer, the compound can be used as a pure material, that is, 100% The ratio is in the hole transport layer, or can be used in combination with one or more other compounds. In a preferred embodiment, the organic layer includes a compound of formula (I) or formula (II), and then additionally includes one or more p-dopants. The p-dopants used according to the present invention are preferably the organic electron acceptor compounds (capable of oxidizing one or more other compounds in the mixture).

Particularly preferred examples of p-dopants are disclosed in WO 2011/073149, EP 1968131, EP 2276085, EP 2213662, EP 1722602, EP 2045848, DE 102007031220, US 8044390, US 8057712, WO 2009/003455, WO 2010 /094378, WO 2011/120709, US 2010/0096600 and WO 2012/095143.

In addition, in this case, the electronic device preferably has a plurality of hole transport layers between the anode and the light emitting layer. It may be that all these layers contain compounds of formula (I) or formula (II), or only individual layers of these layers contain The case of the compound of formula (I) or formula (II).

If the compound of formula (I) or formula (II) is used as the hole transport material, it preferably has a large distance between the HOMO and LUMO energy levels. It is additionally preferred that it does not have any amine group as a substituent. It is additionally preferred that it does not have any substituents on the aromatic ring at all, meaning that R ¹ and R ² are H or D, and more preferably H.

、嘧啶或苯并咪唑。 The compound of formula (I) or formula (II) can additionally be used as an electron transport compound in an electron transport layer, a hole blocking layer or an electron injection layer. For this purpose, preferably the compound of formula (I) or formula (II) contains one or more substituents selected from electron-deficient heteroaryl groups, for example, three

, Pyrimidine or benzimidazole.

The following is a detailed description of generally preferred material categories, which are used as the corresponding functional materials in the organic electroluminescence device of the present invention.

Suitable phosphorescent light-emitting compounds are especially the following compounds. When properly excited, they preferably emit light in the visible light region, and also contain more than 20 atoms, preferably more than 38 and less than 84, more preferably more than 56 and less At least one atom below 80. Preference is given to using compounds containing copper, molybdenum, tungsten, rhenium, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, especially compounds containing iridium, platinum or copper as phosphorescent compounds.

In the context of the present invention, all luminescent iridium, platinum or copper complexes are regarded as phosphorescent compounds.

Examples of the above-mentioned phosphorescent emitters can be found in applications WO 2000/70655, WO 2001/41512, WO 2002/02714, WO Found in 2002/15645, EP 1191613, EP 1191612, EP 1191614, WO 2005/033244, WO 2005/019373 and US 2005/0258742. In general, all phosphorescent composites used in phosphorescent OLEDs according to the prior art and all phosphorescent composites known to those with ordinary knowledge in the field of the invention in the field of organic electroluminescent devices are suitable for use in the device of the present invention. . It is also possible for those with ordinary knowledge in the technical field to which the invention belongs, without using creative skills, to use another phosphorescent compound in combination with the compound of the invention in an OLED.

胺(chrysenamine)或芳族

二胺(chrysenediamine)。芳族蒽胺(anthracenamine)被瞭解為是指其中一個二芳基胺基直接鍵結到蔥基(較佳地在9位置)之化合物。芳族蒽二胺(anthracenediamine)被瞭解為是指其中二個二芳基胺基直接鍵結到蔥基(較佳地在9,10位置)之化合物。芳族芘胺(pyrenamine)、芘二胺(pyrenediamine)、

胺(chrysenamine)及

二胺(chrysenediamine)為被類似地定義，其中，二芳基胺基鍵結到芘(較佳地在1位置或在1,6位置)。又較佳的發射體 為茚并茀胺或茚并茀二胺，舉例而言根據WO 2006/108497或WO 2006/122630、苯并茚并茀胺或苯并茚并茀二胺，舉例而言根據WO 2008/006449、及二苯并茚并茀胺或二苯并茚并茀二胺，舉例而言根據WO 2007/140847、及茚并茀衍生物具有稠合芳基，其係揭露於WO 2010/012328。同樣較佳地為揭露於WO 2012/048780及WO 2013/185871之中之芘芳基胺。同樣較佳地為揭露於WO 2014/037077之苯并茚并茀胺、揭露於尚未公開之EP 13000012.8的苯并茀胺及揭露於尚未公開之EP13004921.6的延伸之茚并茀。 In addition to the compounds of the present invention, preferred fluorescent emission systems are selected from the class of arylamines. In the context of the present invention, arylamine or aromatic amine is understood to mean a compound containing a tri-substituted or unsubstituted aromatic or heteroaromatic ring system directly bonded to nitrogen. Preferably, at least one of these aromatic or heteroaromatic ring systems is a fused ring system, and more preferably has at least 14 aromatic ring atoms. These preferred examples are aromatic anthracenamine (anthracenamine), aromatic anthracene diamine (anthracenediamine), aromatic pyrene amine (pyrenamine), aromatic pyrene diamine (pyrenediamine), aromatic

Amine (chrysenamine) or aromatic

Diamine (chrysenediamine). Aromatic anthracenamines are understood to refer to compounds in which one diarylamine group is directly bonded to an onion group (preferably at the 9 position). Aromatic anthracenediamine (anthracenediamine) is understood to mean a compound in which two diarylamine groups are directly bonded to an onion group (preferably at positions 9, 10). Aromatic pyrenamine (pyrenamine), pyrene diamine (pyrenediamine),

Amine (chrysenamine) and

A diamine (chrysenediamine) is similarly defined in which a diarylamine group is bonded to pyrene (preferably at the 1 position or at the 1, 6 position). Another preferred emitter is indenopyramide or indenopyridiamine, for example, according to WO 2006/108497 or WO 2006/122630, benzindenopyramine or benzindenopyridine diamine, for example According to WO 2008/006449, and dibenzindenopyridine or dibenzindenopyridine diamine, for example, according to WO 2007/140847, and indenopyridine derivatives have condensed aryl groups, which are disclosed in WO 2010/012328. Also preferred is the pyrene arylamine disclosed in WO 2012/048780 and WO 2013/185871. Also preferred are the benzindenolamine disclosed in WO 2014/037077, the benzindenamine disclosed in the unpublished EP 13000012.8, and the extended indenopyramine disclosed in the unpublished EP13004921.6.

The preferred fluorescent compounds are described in the following table:

The preferred matrix material for use in combination with the compound of the present invention as an emitter is selected from the group of oligo-arylene groups (for example, according to EP 676461, 2,2',7,7'-tetraphenylspirodiphenyl or dinaphthalene Anthracene), especially oligo-arylene, oligo-arylene vinylene (such as DPVBi or spiro-DPVBi according to EP 676461), polypodal metal complexes containing fused aromatic groups Substances (for example, according to WO 2004/081017), hole-conducting compounds (for example, according to WO 2004/058911), electron-conducting compounds, especially ketones, phosphine oxides, sulfites, etc. (for example, according to WO 2005/084081 and WO 2005/084082), hindered atropisomers (for example, according to WO 2006/048268), boric acid derivatives (for example, according to WO 2006/117052) or benzanthracenes (For example, according to WO 2008/145239). Particularly preferred matrix materials are selected from: oligo-arylene group, including naphthalene, onion, benzanthracene and/or pyrene or hindered mirror image isomers of these compounds, oligo-arylene ethylene group, ketone, phosphine oxide And Yaqi. The extremely preferred matrix material is selected from the group of oligo-extended aryl groups including onion, benzanthracene, triphenanthrene and/or pyrene or the hindered mirror image isomers of these compounds. An oligoaryl group should be understood in the context of the present invention to mean a compound in which at least three aryl groups or aryl groups are bonded to each other.

The preferred host materials used in the light-emitting layer in combination with the compound of formula (I) or formula (II) are described in the following table:

Suitable charge transport materials that can be used in the hole injection or hole transport layer or electron blocking layer or in the electron transport layer of the electronic device of the present invention are, and the compounds of the present invention, for example disclosed in Y. Shirota et al., Chem. Rev. 2007, 107(4), 953-1010 compound, or other materials used in these layers according to the prior art.

Examples of preferred hole-transporting materials that can be used in the hole-transporting, hole-injecting or electron-blocking layer in the electroluminescent device of the present invention are indene, in addition to the compound of formula (I) or formula (II) Amine derivatives (for example, according to WO 06/122630 or WO 06/100896), amine derivatives disclosed in EP 1661888, hexaazatriphenylene derivatives (for example, according to WO 01 /049806), amine derivatives with fused aromatic systems (for example, according to US 5,061,569), amine derivatives disclosed in WO 95/09147, monobenzoindenopyramine (for example, according to WO 08 /006449), dibenzoindenosylamine (for example, according to WO 07/140847), spirodiamine (for example, according to WO 2012/034627 or WO 2013/120577), stilamine (For example, according to the unpublished applications EP 12005369.9, EP 12005370.7 and EP 12005371.5), spiro dibenzopiperanamine (for example, according to WO 2013/083216) and dihydroacridine derivatives (for example , According to WO 2012/150001).

The preferred cathode of the organic electroluminescence device contains a metal with a low work function, a metal alloy or a multilayer structure composed of various metals, for example, alkaline earth metals, alkali metals, main group metals or lanthanides (such as Ca , Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Additionally suitable are alloys composed of alkali metals or alkaline earth metals and silver, for example, alloys composed of magnesium and silver. In the case of a multilayer structure, in addition to the metal, other metals having a relatively high work function, such as Ag or Al, can also be used. In this case, a combination of metals is usually used, such as, for example, Ca/Ag, Mg/Ag Or Ba/Ag. It may also be preferable to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor. Examples of useful materials for this purpose are alkali metal fluorides or alkaline earth metal fluorides, but also corresponding oxides or carbonates (such as LiF, Li ₂ O, BaF ₂ , MgO, NaF, CsF, Cs ₂ CO _3, etc.) ). It is also possible to use lithium quinolinate (LiQ) for this purpose. The layer thickness of this layer is preferably between 0.5 and 5 nm.

The preferred anode is a material with a high work function. Preferably, the anode has a work function greater than 4.5 eV relative to vacuum. First, metals with a high reduction and oxidation potential are suitable for this purpose, for example, Ag, Pt or Au. Secondly, metal/metal oxide electrodes (such as Al/Ni/NiO _x , Al/PtO _x ) can also be preferred. For some applications, at least one of the electrodes must be transparent or partially transparent for the irradiation of organic materials (organic solar cells) or the emission of light (OLED, O-laser). The preferred anode material here is a conductive mixed metal oxide. Especially preferred is indium tin oxide (ITO) or indium zinc oxide (IZO). The preferred consideration is further conductive doped organic materials, especially conductive doped polymers.

The device is appropriately structured (depending on the application), contact-connected and finally encapsulated, because the life of the device according to the invention is shortened in the presence of water and/or air.

In a preferred embodiment, the organic electroluminescence device according to the present invention is characterized in that one or more layers are coated by sublimation. In this case, the material is applied by vapor deposition in a vacuum sublimation system at an initial pressure of less than 10 ^-5 mbar, preferably less than 10 ^-6 mbar. However, in this case, the initial pressure here may also be even lower, for example lower than 10 ^-7 mbar.

The same priority is given to organic electroluminescence devices, which are characterized in that one or more layers are coated by the OVPD (Organic Vapor Phase Deposition) method or supplemented by the carrier gas sublimation method. In this case, the material is applied at a pressure between 10 ^-5 mbar and 1 bar. A specific example of this method is the OVJP (Organic Vapor Jet Printing) method, in which the material is directly applied via a nozzle and thus structured (for example, MS Arnold et al. , Appl. Phys. Lett. 2008, 92 , 053301).

The preferred consideration is additionally organic electroluminescent devices, which are characterized in that one or more layers are manufactured from solution, for example, by spin coating or Any printing method is used, for example, screen printing, quick-drying printing, nozzle printing or offset printing, but particularly preferably LITI (light-induced thermal imaging, thermal transfer printing) or inkjet printing. For this purpose, soluble compounds of formula (I), or formula (II) are required. High solubility can be achieved by appropriate substitution of compounds.

It is also preferable that the organic electroluminescence device of the present invention is produced by coating one or more layers from a solution and coating one or more layers by sublimation.

According to the present invention, electronic devices comprising one or more compounds of the present invention can be used in displays, as light sources in lighting applications and as light sources in medical and/or cosmetic applications (eg, light therapy).

Working example A) Synthesis example

The procedure is based on the following general reaction diagram:

Similarly, use the following compounds as starting points:

Compound II-a

Ia, 2,8-dibromo-6,12-dihydro-6,6,12,12-tetraoctylindeno[1,2-b]茀, (100g, 116mmol), boric acid diboronic acid pina Alcohol ester (bis (pinacolato) diborane) (64.9 g, 256 mmol) and potassium acetate (75.2 g, 767 mmol) were suspended in 1 L of tetrahydrofuran. The solution was degassed and saturated with argon. After that, PdCl ₂ (dppf)-CH ₂ Cl ₂ (1.9 g, 2.3 mmol) was added. The reaction mixture was heated to boiling for 16 h under a protective gas atmosphere, then cooled to room temperature and concentrated under reduced pressure. The solid is mixed with a mixture of dichloromethane and water and extracted by shaking. The phases were separated and the aqueous phase was extracted twice with dichloromethane. The combined organic phases are washed with water, dried with sodium sulfate, filtered and concentrated under reduced pressure. The crude product was filtered through SiO ₂ /Al ₂ O ₃ with toluene, and then the solvent was removed under reduced pressure. The remaining residue was stirred with methanol and then filtered. The yield was 94.5 g (81% of theory, purity about 95%).

The following products were prepared in a similar manner:

Compound III-a

II-a (85g, 84.6mmol), ethyl 1-bromonaphthalene-2-carboxylate (54.3g, 194mmol) and sodium carbonate (32.5g, 306mmol) were suspended in water/toluene/ethanol (ratio 1:2) : 1,3 l) mixture. The solution was degassed and saturated with argon. Afterwards, tetrakis(triphenylphosphine)palladium(0) (1.95g, 1.7mmol) was added. in The reaction mixture was heated to boiling for 16h under a protective gas atmosphere. The phases were separated and the aqueous phase was extracted twice with toluene. The combined organic phase was washed with water, dried with sodium sulfate, filtered and then concentrated under reduced pressure. The mixture was filtered with toluene through Celite and then the solvent was removed under reduced pressure. The remaining residue was stirred with methanol and then filtered. The yield was 89.0 g (96% of theory).

The following products were prepared in a similar manner:

Compound IV-a

At a temperature between 0°C and 5°C, a mixture of anhydrous cerium chloride (41.9g, 170mmol) and 500ml of anhydrous tetrahydrofuran was added dropwise to III-a (89g, 81mmol) in 1 l of anhydrous tetrahydrofuran. The reaction mixture was stirred at this temperature for 1 h. Afterwards, 400 ml of saturated aqueous ammonium chloride solution was added dropwise at a temperature between 0°C and 20°C. Filter the resulting suspension. Then the phases were separated and the aqueous phase was extracted twice with 200 ml of ethyl acetate. The combined organic phase was concentrated under reduced pressure. The yield was 59.8 g (69% of theory).

The following products were prepared in a similar manner:

Compound V-a

A mixture of methanesulfonic acid (10.8ml, 16mmol) to polyphosphoric acid (16.4g, 167mmol) and 700ml of dichloromethane was added dropwise at a temperature of 0°C. After that, a suspension of IV-a (59.8 g, 56 mmol) in 800 ml of dichloromethane was slowly added dropwise at 0°C. The reaction mixture was stirred at 0°C for 2h. 800 ml of ethanol was added and then the reaction mixture was stirred for 30 minutes. The solvent was removed under reduced pressure and the remaining residue was recrystallized twice with a mixture of toluene and heptane. The yield was 46.3 g (80% of theory).

The following products were prepared in a similar manner:

Compound VI-a

Va (41.3 mg, 40 mmol) was dissolved in 1 l of dichloromethane. Then, at 0°C, Br ₂ (12.74 g, 79.7 mmol) in 300 ml of dichloromethane was added dropwise. The reaction mixture was stirred at room temperature overnight. 200 ml of sodium thiosulfate solution was added and the reaction mixture was stirred for 30 minutes. After that, the phases are separated. The organic phase was washed with water, dried with sodium sulfate and concentrated by rotary evaporation. The reaction mixture was filtered with toluene through SiO ₂ and Al ₂ O ₃ and concentrated by rotary evaporation. The remaining residue was recrystallized twice with toluene/heptane. The yield was 40.8 g (86% of theory).

Compound VII-a

VI-a (20g, 16.5mmol), dibenzofuran-4-ylboronic acid (7.7g, 36.3mmol) and tripotassium phosphate monohydrate (15.2g, 66mmol) were suspended in toluene/dioxane (dioxane)/water (1:1:1, 600ml) mixture. After that, palladium acetate (74 mg, 0.33 mol) and tris( o- tolyl)phosphine (602 mg, 2.0 mmol) were added. The reaction mixture was heated to boiling for 16h. After the reaction mixture was cooled to room temperature, the organic phase was extended with 300 ml of ethyl acetate. The phases were separated and the aqueous phase was extracted twice with ethyl acetate. The combined organic phase was dried over sodium sulfate and then concentrated under reduced pressure. The mixture was filtered through alumina with toluene and then recrystallized repeatedly with toluene/heptane to the remaining residue. The yield was 18.3 g (82% of theory).

The following compounds were prepared in a similar manner:

B) Launch data

The compound of formula (I) or formula (II) is dissolved in toluene, and then the absorption spectrum and/or photoluminescence spectrum of the compound of formula (I) or formula (II) is recorded.

The absorption spectrum was measured on a Lambda 9 instrument, UV/VIS/NIR spectrometer (from Perkin Elmer). The photoluminescence spectrum was measured on the F-4500 instrument, a fluorescence spectrophotometer (from Hitachi).

B-1) Comparative compound (1) emission data

B-2) Emission data of target compound (1)

¹ : Absorption measurement

² : Emission measurement

³ : The maximum value of absorption and emission peaks is in nm; the initial maximum (nm) plus the bottom line

Upon excitation, the comparative compound (1) based on the basic skeleton of benzindenopyridine emits ultraviolet and violet light at wavelengths of 409 nm, 432 nm and 458 nm.

It has now surprisingly been found that the compound of formula (I) or formula (II) of the present invention based on the extended bis-indenopyridine basic skeleton has emission shifted to a larger wavelength. The target compound (1) particularly has an emission partly falling in the wavelength range of blue visible light. Therefore, the target compound 1 has emission peaks at 420 nm, 445 nm and 473 nm.

Therefore, the target compound (1) has blue emission when excited and is therefore suitable for use as a blue single-peak emitter in electronic devices.

c) Device embodiment: production of OLED

The OLED of the present invention and the OLED according to the prior art are produced by the general method according to WO 2004/058911. The production of solution-based OLEDs is described, for example, in WO 2004/037887 and in WO 2010/097155. In the following embodiment, the two production methods are combined so that a layer including the OLED emission layer is processed from solution, and the subsequent layer (such as the electron transport layer of the OLED) is applied by vapor deposition under reduced pressure. The above general methods are combined as follows and conform to the environment described here (variation of layer thickness, materials).

In the following examples (see Tables 1 and 2), data of various OLEDs are presented. The substrate used is a glass substrate coated with structured ITO (Indium Tin Oxide) with a thickness of 50 nm. OLED basically has the following layer structure: substrate/buffer layer (20nm)/hole transport layer (HTL, 20nm)/emission layer (EML, 60nm)/electron transport layer (ETL, 20nm)/electron injection layer (EIL, 3nm) and finally the cathode. The cathode is formed by an aluminum layer with a thickness of 100 nm. The substrate was coated with a buffer layer of Pedot: PSS (poly(3,4-ethylenedioxy-2,5-thiophene) polystyrene sulfonate), purchased from Heraeus Precious Metals GmbH & Co. KG. Spin coating from water under air. The layers are baked sequentially at 180°C for 10 minutes. The hole transport layer and the emission layer are applied to the substrate thus coated. The structure of the OLED material is shown in Table 2, where HTL represents the material of the hole transport layer, where EIL represents the material of the electron injection layer, and where ETL represents the material of the electron transport layer.

The hole transport layer is composed of polymer HTL and has the structure shown in Table 2, which is synthesized according to WO 2010/097155. The polymer was dissolved in toluene so that the solution had a solid content of about 5 g/l to achieve a layer thickness of 20 nm by spin coating. In this example, the layer is rotated under an inert gas argon atmosphere and baked at 180°C for 60 minutes.

The emission layer (EML) is always composed of at least one host material (host=H) and a light-emitting compound (emitter, dopant=D) (added to the host material in a special weight ratio). The details given in this form H1: D1 (92%: 8%) here means that the host material H1 is present in the emitting layer at a weight ratio of 92% and the luminescent compound D1 is at a weight ratio of 8%. The mixture of the emitting layer is dissolved in the nail Benzene, so that the solution has a solid content of about 18g/l, the layer thickness is 60nm by spin coating. In this example, the layer is rotated under an inert gas argon atmosphere and baked at 140°C for 10 minutes. The host material H and the dopant D used are shown in Table 1. The material structure used for the OLED emission layer is shown in Table 2.

The materials of the electron transport layer and the cathode are applied by thermal vapor deposition in a vacuum chamber. For example, the electron transport layer can be composed of more than one material, and the materials are added to each other by co-evaporation in a special volume ratio. The details given in this form of ETM: EIL (50%: 50%) mean that the ETM and EIL materials are each present in the layer in a volume ratio of 50%. In this example, the electron transport layer is composed of a matrix material ETL with a layer thickness of 20 nm and an electron injection layer (composed of a material EIL with a layer thickness of 3 nm). The material ETL and material EIL are shown in Table 2.

Characterize the OLED in a standard way. For this purpose, record the electroluminescence spectrum, and assume the Lambertian emission characteristics, calculate the current efficiency (measured in cd/A) and the external quantum efficiency (EQE, measured in percentage) from the current-voltage-luminance characteristic (IUL characteristic) as the luminance Function, and finally determine the component life. Record the electroluminescence spectrum with a brightness of 1000cd/m ² , and calculate the CIE 1931 x and y color coordinates from it. The parameter EQE @ 1000cd/m ² refers to the external quantum efficiency at the operating brightness of 1000cd/m ² . The operating life of the current density of 10mA / cm Time elapsed before LD80 @ 10mA initial luminance decreased by 20% at ² / cm ^2. The data obtained for various OLEDs are summarized in Table 1.

D) Use of the compounds of the invention as emitters in fluorescent OLEDs

The compounds D1, D2, D3 and D4 of the present invention are individually used as emitters in the OLED light-emitting layer (see Table 2 for the structure). The host material used for the light-emitting layer is compound H1 or H2. The resulting OLEDs are I1 to I6. Its dark blue emission exhibits a very good lifetime (LD80) (Table 1). Compared with the emitter materials known in the prior art (C-D1 and C-D2; references C1 to C3), the quantum efficiency is improved and the lifetime (LD80) is significantly improved.

In particular, the comparison with the material C-D2 shows the improvement achieved by the extended bis-indeno pyridine basic skeleton of the present invention compared with the bis-indeno pyridine basic skeleton known in the prior art.

In addition, the compounds of the present invention have good solubility in non-polar solvents, so they are suitable for processing from solutions. Therefore, an electronic device with a blue-fluorescent emitter is obtained, which has superior performance data.

Alternatively or additionally, the compound of the present invention can also be used as the matrix material in the emission layer (EML) of OLED, as the hole transport material in the hole transport layer (HTL), and as the electron transport material in the electron transport layer (ETL) Or as the hole injection material in the hole injection layer (HIL).

Claims (17)

A compound of formula (II-1) or formula (II-2)

Wherein: Z ¹ is the same or different in each case and is CR ¹ or N, wherein when a group is attached, Z ¹ is C; Z ² is the same or different in each case and is CR ² or N, where when a group is attached, Z ² is C; X ¹ is the same or different in each case and is BR ³ , C(R ³ ) ₂ , C(R ³ ) ₂ -C(R ³ ) ₂ , -C(R ³ ) ₂ -O-, -C(R ³ ) ₂ -S, -R ³ C=CR ³ -, -R ³ C=N-, Si(R ³ ) ₂ , Ge( R ³ ) ₂ , -Si(R ³ ) ₂ -Si(R ³ ) ₂ -, C=O, O, S, Se, S=O, SO ₂ , NR ³ , PR ³ or P(=O)R ³ , wherein two or more R ³ groups can be combined with each other and can form a ring; R ¹ , R ² , R ³ are the same or different in each case and are H, D, F, Cl, Br, I , C(=O)R ⁴ , CN, Si(R ⁴ ) ₃ , N(R ⁴ ) ₂ , P(=O)(R ⁴ ) ₂ , OR ⁴ , S(=O)R ⁴ , S(= O) ₂ R ⁴ , linear alkyl or alkoxy having 1 to 20 carbon atoms, branched or cyclic alkyl or alkoxy having 3 to 20 carbon atoms, having 2 to 20 carbon atoms The alkenyl or alkynyl group, the aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, or the aryloxy or heteroaryloxy group with 5 to 30 aromatic ring atoms, wherein, the above each group may be substituted with one or more substituents R ^4, wherein one or more of the above groups a CH ₂ group may be ^{-R 4 C = CR 4 -,} - C≡C-, Si (R 4 ) ₂ , C=O, C=NR ⁴ , -C(=O)O-, -C(=O)NR ⁴ -, NR ⁴ , P(=O)(R ⁴ ), O, S, SO or SO ₂ replacement, wherein one or more of the hydrogen atoms in the above groups can be replaced by D, F, Cl, Br, I or CN, and wherein two R ³ groups can be combined with each other and can form a ring; R ⁴ It is the same or different in each case and is H, D, F, Cl, Br, I, C(=O)R ⁵ , CN, Si(R ⁵ ) ₃ , N(R ⁵ ) ₂ , P(= O)(R ⁵ ) ₂ , OR ⁵ , S(=O)R ⁵ , S(=O) ₂ R ⁵ , straight-chain alkyl or alkoxy with 1 to 20 carbon atoms, with 3 to 20 Branched or cyclic alkyl or alkoxy of carbon atoms, alkenyl or alkynyl with 2 to 20 carbon atoms, aromatic or heteroaromatic ring system with 5 to 30 aromatic ring atoms, or 5 Aryloxy or heteroaryloxy with up to 30 aromatic ring atoms, wherein the above-mentioned groups may each be substituted by one or more R ⁵ groups, wherein one or more of the above-mentioned groups are CH ₂ groups Can be passed -R ⁵ C=CR ⁵ -, -C≡C-, Si(R ⁵ ) ₂ , C=O, C=NR ⁵ , C(=O)O, -C(=O)NR ⁵ -, NR ⁵ , P(=O) (R ⁵ ), O, S, SO, or SO ₂ replacement, wherein one or more of the hydrogen atoms in the above groups can be replaced by D, F, Cl, Br, I, or CN, and wherein, two or more Each R ⁴ group can be combined with each other and can form a ring; R ⁵ is the same or different in each case and is H, D, F, Cl, Br, I, CN, a straight chain alkane having 1 to 20 carbon atoms Group or alkoxy group, branched or cyclic alkyl group or alkoxy group having 3 to 20 carbon atoms, alkenyl or alkynyl group having 2 to 20 carbon atoms, those having 5 to 30 aromatic ring atoms or an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms of an aryl group or a heteroaryl group, wherein two or more R ⁵ groups may be bonded to each other may form a ring. For example, the compound of item 1 in the scope of the patent application, wherein X ¹ is the same or different in each case and is selected from C(R ³ ) ₂ , -C(R ³ ) ₂ -C(R ³ ) ₂ -, -C(R ³ ) ₂ -O-, Si(R ³ ) ₂ , O, S, and NR ³ , wherein two or more R ³ groups can be combined with each other and can form a ring. For example, the compound of item 2 in the scope of patent application, wherein X ¹ is C(R ³ ) ₂ . Such as the compound of item 1 in the scope of patent application, wherein R ¹ is the same or different in each case and is selected from H, CN, N(R ⁴ ) ₂ and aromatics having 5 to 30 aromatic ring atoms Or a heteroaromatic ring system, wherein the above groups can each be substituted with one or more R ⁴ groups. Such as the compound of item 1 in the scope of patent application, wherein R ² is H or D. Such as the compound of item 1 in the scope of the patent application, wherein R ³ is the same or different in each case and is selected from a linear alkyl group having 1 to 20 carbon atoms or a branched chain having 3 to 20 carbon atoms alkyl. For example, the compound of item 1 in the scope of patent application, wherein the compound corresponds to one of the following formulas (D1) to (D4)

An oligomer comprising a compound as described in any one of items 1 to 7 in the scope of the patent application, wherein the bond to the oligomer can be located at any desired position, which is represented by formula (II-1) or formula ( R ¹ or R ² in II-2) is substituted. A polymer comprising a compound as described in any one of items 1 to 7 in the scope of the patent application, wherein the bond to the polymer can be located at any desired position, which is represented by formula (II-1) or formula (II- 2) The R ¹ or R ^{2 is} substituted. A dendritic polymer, comprising a compound as in any one of items 1 to 7 in the scope of the patent application, wherein the bond to the dendrimer can be located at any desired position, which is represented by formula (II-1) or R ¹ or R ^{2 in} formula (II-2) is substituted. A formulation, including, for example, the compound of any one of the scope of patent application from 1 to 7, the oligomer of the scope of patent application of item 8, the polymer of patent application of item 9 or the 10th patent application. The dendritic polymer and at least one solvent. An electronic device selected from the group consisting of organic integrated circuits (OIC), organic field effect transistors (OFET), organic thin film transistors (OTFT), organic light emitting transistors (OLET), organic solar cells ( OSC), organic optical detector, organic photoreceptor, organic field quenching device (OFQD), organic light-emitting electrochemical element (OLEC), organic laser diode (O-laser) and organic electroluminescent devices (OLED), including compounds in any one of the scope of patent applications from 1 to 7, oligomers in the scope of patent applications, and oligomers in the scope of patent applications. 9 polymers or dendrimers such as the 10th patent application. For example, the electronic device of item 12 of the patent application is selected from organic electroluminescence devices, including a cathode, an anode, and at least one organic layer, wherein the at least one organic layer includes any one of items 1 to 7 in the scope of the patent application The compound of the item, such as the oligomer of the 8th patent application, the polymer of the 9th patent application or the dendrimer of the 10th patent application. Such as the electronic device of the 13th patent application, such as the compound of any one of the 1st to the 7th patent application, the oligomer of the 8th patent application, and the polymerization of the 9th patent application Substances or dendrimers as in the tenth item of the scope of patent application exist as hole-transporting materials in the hole-transporting layer, as luminescent compounds in the light-emitting layer or as host compounds in the light-emitting layer. Such as the electronic device of item 14 of the scope of patent application, wherein the compound exists as a light-emitting compound in the light-emitting layer. A compound such as any one of items 1 to 7 of the patent application, or an oligomer such as the eighth patent application, a polymer such as the 9 patent application or a dendrimer such as the tenth patent application The use of crystalline polymers in electronic devices. A method for preparing a compound according to any one of items 1 to 7 in the scope of the patent application, wherein the method includes at least one metal-catalyzed coupling Reaction and at least one ring-closing reaction.